CN109439914B - Method for selectively separating lithium from leachate of anode material of waste lithium ion battery - Google Patents
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Abstract
The invention discloses a method for selectively separating lithium from a leachate of a positive electrode material of a waste lithium ion battery, belonging to the field of regeneration of useful parts of waste storage batteries. The invention adopts crown ether compound with selective recognition function to lithium ion as adsorbent, and dissolves in certain organic solvent to extract lithium ion, thereby realizing selective separation of lithium ion, being capable of extracting lithium ion from complex solution containing metal ions such as cobalt, nickel, manganese, iron, etc., having high recovery rate and strong selectivity, and the extracted organic phase can be reused after back extraction.
Description
Technical Field
The invention belongs to the field of regeneration of useful parts of waste storage batteries, and particularly relates to a method for selectively separating lithium from a leachate of a positive electrode material of a waste lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, low self-discharge rate, good safety, no memory effect and the like, and is widely applied to the fields of mobile phones, notebook computers, portable tools and the like. Since the lithium ion battery enters commercialization in the 90 th of the 20 th century, a large amount of waste lithium ion batteries have been generated so far, and with the rapid development of electric automobiles in recent years, China will come up with a large-scale scrapping period of power lithium ion batteries after 2020. The anode material of the waste lithium ion battery contains various valuable metal elements such as lithium, cobalt, nickel, manganese, iron and the like, and if the valuable metal elements are not effectively recovered, the waste of resources is greatly caused.
At present, in the treatment of the anode materials of waste lithium ion batteries, sulfuric acid, hydrochloric acid or nitric acid is mainly adopted for leaching, and then various metal ions are recovered from the leachate by methods such as precipitation, extraction, electrodeposition and the like. The method for recovering lithium from the leachate of the positive electrode material of the waste lithium ion battery mainly comprises two methods, namely a sodium carbonate precipitation method and a lithium ion sieve adsorption method.
Through search, chinese patent publication No. CN 1601805a discloses a method for recovering and treating waste lithium ion batteries, which combines a precipitation method and an extraction method to remove cobalt and copper in a leaching solution, and then adds sodium carbonate into a raffinate to precipitate lithium, so that lithium is recovered in the form of lithium carbonate precipitate. However, lithium carbonate has a certain solubility in an aqueous solution, and the solubility thereof is reduced with the increase of the solution temperature, so that the lithium precipitation by using sodium carbonate must be carried out at a temperature of more than 90 ℃, the energy consumption is high, and the recovery cost is increased.
The Chinese patent application numbers are: 201710745571.1, published as 2018, 2/13, discloses a method for extracting lithium from wastewater by an extraction method, which comprises the following steps: directly mixing the lithium-containing wastewater with an extracting agent (wherein the extracting agent is one or a mixture of more of a copper extracting agent, n-octanol, isooctanol, sulfonated kerosene, lauryl alkyl, alkyl phosphoric acid, phosphorus oxide, diketone and crown ether), and then clarifying, wherein the weight ratio of the lithium-containing wastewater to the extracting agent is 1 (1-4), and the extraction rate reaches 99 percent through four-stage extraction; the extracted oil machine is subjected to back extraction by using 3N-6N hydrochloric acid to obtain a lithium chloride solution, and the weight ratio of the oil machine to the hydrochloric acid is 1 (1-4); and then directly adding the lithium chloride solution into the saturated sodium carbonate solution, separating by using a centrifugal machine, and washing to obtain a lithium carbonate product, wherein the weight ratio of the potassium chloride solution to the saturated sodium carbonate solution is 1 (1-4). However, it has to be mentioned: although crown ether is mentioned as an extractant of lithium in lithium-containing wastewater, the components of the lithium-containing wastewater and the types of the crown ether are not specified, actually, the adsorption mechanism of the crown ether on metal ions is extremely complex, the types of the crown ether are more than hundreds, the types of the lithium-containing aqueous solution are also extremely rich, the selective extraction of lithium can be realized only when the types of the crown ether and the lithium-containing aqueous phase components are completely matched, and the crown ether can not realize the selective extraction of lithium in most of the time, so the guidance of the patent on the extraction of lithium in a specific solution is very limited. In addition, in the above patent, after lithium in the aqueous phase is extracted, the aqueous solution of lithium chloride is obtained by back-extracting with hydrochloric acid of high concentration (3N to 6N), and then lithium is precipitated and recovered from the aqueous solution of lithium chloride by using sodium carbonate. On one hand, a large amount of high-concentration hydrochloric acid is consumed to pollute the environment, and on the other hand, the problem of low recovery rate of lithium precipitated from a water phase cannot be solved. In addition, when the above patent is used for extracting lithium, the pH value needs to be adjusted to an alkaline environment of 7-13, and the leachate of the anode material of the waste lithium ion battery is acidic, so that if lithium in the waste lithium ion battery is recovered by the method, a large amount of alkaline solution is needed to adjust the pH value.
Chinese patent publication No. CN 1200475C discloses a method for separating and recovering lithium from waste lithium ion batteries by using an ion sieve, which utilizes lambda-MnO2Method for selectively adsorbing lithium ions from waste lithium ion battery acid leaching solution by using ion sieve as adsorbent, so that lithium ions are adsorbed to lambda-MnO2And eluting with dilute hydrochloric acid solution after the crystal gaps of the ion sieve, thereby realizing the purpose of separating and recovering lithium. However, the lithium ion sieve has unstable properties and poor reusability, and particularly has high dissolution loss rate in the acid washing process, so that a great amount of adsorbent is lost.
In addition, the first and third methods can be performed after removing other impurity ions in the leachate, and cannot be directly used for extracting lithium from a complex solution containing metal ions such as cobalt, nickel, manganese, iron, and the like. Therefore, new technologies must be developed to achieve selective separation and stable and efficient extraction of lithium from complex lithium-containing feed solutions.
Disclosure of Invention
1. Problems to be solved
The invention provides a method for selectively separating lithium from a leachate of a positive electrode material of a waste lithium ion battery, aiming at the problems of low recovery rate, low selectivity and unstable lithium ion sieve adsorbent property in the existing method when the lithium is recovered from the leachate of the positive electrode material of the waste lithium ion battery.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for selectively separating lithium from a leachate of a positive electrode material of a waste lithium ion battery comprises the following steps:
(1) dissolving crown ether compound in organic solvent to prepare extractant;
(2) mixing the extractant prepared in the step (1) with the positive electrode material leaching solution of the waste lithium ion battery, and then separating to obtain a lithium-rich organic phase and a water phase;
(3) and (3) carrying out back extraction-precipitation treatment on the lithium-rich organic phase in the step (2) by adopting a saturated sodium carbonate solution, and filtering to obtain a lithium carbonate precipitate.
Preferably, the crown ether compound in the step (1) is one of benzo 15-crown-5 and derivatives thereof and dibenzo 14-crown-4 and derivatives thereof; wherein, the benzo 15-crown-5 derivative is obtained by replacing hydrogen on a benzo 15-crown-5 benzene ring by one of hydroxyl, amino, hydroxyl-substituted methyl and amino-substituted methyl; the dibenzo 14-crown-4 derivative is obtained by substituting hydrogen on a benzene ring at one side of the dibenzo 14-crown-4 by one of hydroxyl, amino, hydroxyl-substituted methyl and amino-substituted methyl.
Preferably, the organic solvent in step (1) is one of sulfonated kerosene, dichloromethane, n-heptane, cyclohexane and nitrobenzene.
Preferably, the mass percentage of the crown ether compound in the organic solvent is 10-30%.
Preferably, the positive electrode material in the step (2) is one or a combination of two or more of lithium cobaltate, lithium manganate, lithium nickelate, ternary positive electrode material (lithium nickel cobalt manganate) and lithium iron phosphate positive electrode material.
Preferably, the leachate in step (2) is a filtrate obtained by leaching the cathode material in hydrochloric acid, sulfuric acid or nitric acid.
Preferably, the leaching solution in the step (2) contains 0.5-10g/L of Li, 0-80 g/L of Co and Ni0 to 80g/L, Mn0 to 80g/L, Fe 0 to 80g/L, and a hydrogen ion concentration of 10-6And the pH value ranges from-0.8 to 6 when the concentration is about 6 mol/L.
Preferably, the step (2) adopts single-stage extraction, 2-10 stages of multi-stage cross-flow extraction or 2-10 stages of multi-stage counter-current extraction.
Preferably, in the step (2), the extraction temperature is 25-80 ℃, the extraction ratio is 1 (0.5-5), and the extraction time is 10-60 min.
Preferably, the temperature of the back extraction-precipitation in the step (3) is 25-95 ℃, the volume ratio of the saturated sodium carbonate solution to the lithium-rich organic phase is 1 (0.5-2), and the time is 10-60 min.
Crown ether compounds, particularly crown ethers of relatively simple structure such as benzo 15-crown-5 and dibenzo 14-crown-4, have certain water solubility and are therefore easily lost during use, and at the same time, have limited solubility in the organic phase, thus resulting in large amounts of organic solvents. The solution is given in the literature 'research on performance of separating lithium isotope by benzo 15-crown-5 ether grafted chitosan film' (great swallow, severe peak, Li Jian Xin, Chi Sha Yu, where bridge. research on performance of separating lithium isotope by benzo 15-crown-5 ether grafted chitosan film [ J ] high molecular science, 2017 (12): 1967-: the benzo 15-crown-5 ether is immobilized on a chitosan film for solid-liquid extraction. However, on one hand, the preparation process of the adsorbent is complex and difficult to apply on a large scale, and on the other hand, the crown ether solid loading is small, so that the adsorption capacity is reduced, and therefore, the method is only suitable for small-scale application fields such as lithium isotope separation and the like, but is not suitable for separating lithium from a large amount of lithium-containing water phase. While the literature, "research on the synthesis of dibenzo-14-crown-4 by ultrasonic waves and its application in lithium-magnesium separation" (Zhao Xiao le, Liang Qu, Chuai Jing. dibenzo-14-crown-4 by ultrasonic waves and research on the separation of lithium and magnesium [ J ]. chemical research and application, 2016, 28 (08): 1098-. In order to increase the extraction rate of lithium, the solution given in this document is to add di (2-ethylhexyl) phosphonate to the extractant to achieve synergistic extraction, which can increase the lithium magnesium separation coefficient to 6.17. The benzene ring of the benzo 15-crown-5 and the derivative thereof and the dibenzo 14-crown-4 and the derivative thereof adopted by the invention has additional functional groups (namely hydroxyl, amino, hydroxymethyl and amino substituted methyl) shown in figure 1, so that the water solubility can be effectively reduced, and the solubility in an organic phase is enhanced, thereby avoiding the loss of crown ether and reducing the dosage of an organic solvent. In addition, the functional groups are electron-donating groups, and the coordination capacity between the crown ether ring and lithium ions can be enhanced, so that the extraction rate of lithium is greatly improved, and the separation coefficient of lithium and impurity ions is improved to more than 100.
In addition, the selective adsorption capacity of crown ether on metal ions in a solution is closely related to various factors such as the size of the ring aperture of the crown ether, the radius of the metal ions, the hardness, the acid-base properties of the metal ions and the like. According to the invention, a large amount of experimental research and theoretical calculation are carried out based on the soft and hard acid-base theory, the size of crown ether and the like, and then the finding is that only benzo 15-crown-5 and the derivatives thereof and dibenzo 14-crown-4 and the derivatives thereof can be well matched with lithium ions on the aperture size and the soft and hard acid-base properties aiming at the water phase containing lithium, cobalt, nickel, manganese and iron, and the matching with cobalt, nickel, manganese and iron is poor, so that the selective adsorption effect on lithium in the water phase is realized, and the type of crown ether is specifically limited.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for selectively separating lithium from the leachate of the anode material of the waste lithium ion battery, the adopted crown ether compound has selective recognition capability on lithium ions in the solution, so that the extraction of the lithium ions from the complex solution containing various metal ions such as cobalt, nickel, manganese, iron and the like can be realized, and the extraction of the lithium can be realized only after other metal ions except the lithium are separated by the traditional method;
(2) according to the method for selectively separating lithium from the leachate of the anode material of the waste lithium ion battery, the adopted crown ether compound has strong binding capacity to lithium ions in the solution, so that the adsorption separation of lithium can be still realized when the concentration of the lithium ions in the solution is lower, and more than 99% of lithium in the solution can be transferred to an organic phase;
(3) according to the method for selectively separating lithium from the leachate of the anode material of the waste lithium ion battery, the crown ether compound is dissolved in the organic phase to extract lithium ions, and the organic phase can be repeatedly used after being reversely extracted, so that the use cost of the adsorbent is reduced;
(4) according to the method for selectively separating lithium from the leachate of the anode material of the waste lithium ion battery, the saturated sodium carbonate solution is adopted to precipitate lithium from the organic phase, and the lithium carbonate has low solubility in the organic phase, so that the precipitation rate of lithium is high, and the recovery rate can reach more than 95%.
Drawings
FIG. 1 chemical structural formula of crown ether compound used in the present invention;
fig. 2 is an XRD pattern of lithium carbonate prepared by the present invention.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The sulfuric acid leaching solution of the anode material of the waste lithium ion battery is used as a raw material, the pH value of the sulfuric acid leaching solution is 6, and the components are 0.5g/L of Li and 4.2g/L of Co. Dissolving certain benzo 15-crown-5 in sulfonated kerosene to prepare an extraction organic phase with crown ether mass fraction of 10%. The single extraction was carried out at a temperature of 80 deg.C compared to 2:1 for 10 min. And (3) after the organic phase and the water phase are separated, back-extracting for 10min at the temperature of 25 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 2:1 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 95.3%. As shown in fig. 2, the XRD pattern of the obtained lithium carbonate is clear that there is no impurity peak, indicating that the obtained lithium carbonate has high purity and contains no impurity phase.
Example 2
The hydrochloric acid leachate of the anode material of the waste lithium ion battery is used as a raw material, the hydrogen ion concentration of the hydrochloric acid leachate is 6mol/L, and the hydrochloric acid leachate comprises Li 8.3g/L, Co 22.5g/L, Ni 23.8g/L and Mn 21.3 g/L. Dissolving a certain amount of 4-aminobenzene 15-crown-5 in sulfonated kerosene to prepare an extraction organic phase with crown ether mass fraction of 30%. Performing 10-stage cross-flow extraction at 25 deg.C for 60min compared with 1: 5. And (3) after the organic phase and the water phase are separated, back-extracting for 60min at the temperature of 95 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 2:1 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 98.1%.
Example 3
The sulfuric acid leaching solution of the anode material of the waste lithium ion battery is used as a raw material, the pH value of the sulfuric acid leaching solution is 1, and the components are Li 5.3g/L and Mn 80 g/L. Dissolving a certain amount of 4-hydroxybenzene 15-crown-5 in dichloromethane to prepare an extraction organic phase with crown ether mass fraction of 15%. Performing 10-stage countercurrent extraction at 30 deg.C for 45min compared with 2: 1. And (3) after the organic phase and the water phase are separated, back-extracting for 50min at the temperature of 25 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 1:2 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 96.6%.
Example 4
The hydrochloric acid leachate of the anode material of the waste lithium ion battery is used as a raw material, the pH value of the hydrochloric acid leachate is 0, and the components are Li 9.2g/L and Ni 80 g/L. Dissolving a certain amount of 4-hydroxymethylbenzo 15-crown-5 in n-heptane to prepare an extraction organic phase with crown ether mass fraction of 20%. Carrying out 3-stage cross-flow extraction at 40 ℃ for 30min compared with 2: 1. And (3) after the organic phase and the water phase are separated, back-extracting for 30min at the temperature of 45 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 1:1 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 95.4%.
Example 5
Takes nitric acid leachate of the anode material of the waste lithium ion battery as a raw material, and has the pH value of 4.5 and the components of Li 10g/L and Fe80 g/L. Dissolving a certain amount of 4-aminomethyl benzo 15-crown-5 in cyclohexane to prepare an extraction organic phase with crown ether mass fraction of 30%. Performing 8-stage countercurrent extraction at 35 deg.C for 50min, compared with 2: 1. And (3) after the organic phase and the water phase are separated, back-extracting for 30min at the temperature of 45 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 2:1 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 96.8%.
Example 6
The sulfuric acid leaching solution of the anode material of the waste lithium ion battery is used as a raw material, the pH value of the sulfuric acid leaching solution is 0.5, and the components are Li 8.6g/L, Co 25.8g/L, Ni 8.1g/L, Mn 4.7g/L and Fe 30.7 g/L. Dissolving certain dibenzo 14-crown-4 in sulfonated kerosene to prepare an extraction organic phase with crown ether mass fraction of 28%. Carrying out 5-stage cross-flow extraction at 65 ℃ for 50min compared with 1: 3. And (3) after the organic phase and the water phase are separated, back-extracting for 45min at the temperature of 70 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 2:1 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 98.3%.
Example 7
The sulfuric acid leaching solution of the anode material of the waste lithium ion battery is used as a raw material, the pH value of the sulfuric acid leaching solution is 5, and the components are Li 3.5g/L, Co 16.5g/L and Fe 12.2 g/L. Dissolving a certain amount of 4-aminodibenzo 14-crown-4 in sulfonated kerosene to prepare an extraction organic phase with crown ether mass fraction of 10%. Performing 3-stage countercurrent extraction at 65 deg.C for 30min compared with 1: 1. And (3) after the organic phase and the water phase are separated, back-extracting for 35min at the temperature of 40 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 1:1 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 97.5%.
Example 8
The sulfuric acid leaching solution of the anode material of the waste lithium ion battery is used as a raw material, the pH value of the sulfuric acid leaching solution is 3.5, and the components are Li 5.4g/L, Co 29.2g/L, Ni 8.3g/L and Mn 15.8 g/L. Dissolving certain 4-hydroxy dibenzo 14-crown-4 in nitrobenzene to prepare an extraction organic phase with crown ether mass fraction of 25%. Carrying out 6-stage cross-flow extraction at 75 ℃ for 50min compared with 1: 4. And (3) after the organic phase and the water phase are separated, back-extracting for 25min at the temperature of 80 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 1:1 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 96.4%.
Example 9
The hydrochloric acid leachate of the anode material of the waste lithium ion battery is used as a raw material, the hydrogen ion concentration of the hydrochloric acid leachate is 3mol/L, and the components are Li 7.6g/L, Co 22.4g/L, Ni 6.1g/L, Mn 9.6g/L and Fe 25.5 g/L. Dissolving a certain amount of 4-hydroxymethyl dibenzo 14-crown-4 in sulfonated kerosene to prepare an extraction organic phase with crown ether mass fraction of 30%. Performing 8-stage countercurrent extraction at 35 deg.C for 45min compared with 2: 1. And (3) after the organic phase and the water phase are separated, back-extracting for 50min at the temperature of 40 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 2:1 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 95.9%.
Example 10
The hydrochloric acid leachate of the anode material of the waste lithium ion battery is used as a raw material, the pH value of the hydrochloric acid leachate is 2.5, and the hydrochloric acid leachate comprises components of 2.1g/L of Li, 13.6g/L of Co, 3.4g/L of Ni and 1.8g/L of Mn. Dissolving a certain amount of 4-aminomethyl dibenzo 14-crown-4 in sulfonated kerosene to prepare an extraction organic phase with crown ether mass fraction of 10%. Carrying out 4-stage cross-flow extraction at 35 ℃ for 35min compared with 1: 3. And (3) after the organic phase and the water phase are separated, back-extracting for 20min at the temperature of 65 ℃ under the condition that the volume ratio of the saturated sodium carbonate solution to the organic phase is 1:1 to obtain white lithium carbonate precipitate, wherein the recovery rate of lithium reaches 96.8%.
Claims (9)
1. A method for selectively separating lithium from a leachate of a positive electrode material of a waste lithium ion battery is characterized by comprising the following steps of: the method comprises the following steps:
(1) dissolving crown ether compound in organic solvent to prepare extractant;
(2) mixing the extractant prepared in the step (1) with the positive electrode material leaching solution of the waste lithium ion battery, and then separating to obtain a lithium-rich organic phase and a water phase;
(3) carrying out back extraction-precipitation treatment on the lithium-rich organic phase in the step (2) by adopting a saturated sodium carbonate solution, and filtering to obtain a lithium carbonate precipitate; the crown ether compound in the step (1) is one of benzo 15-crown-5 and derivatives thereof and dibenzo 14-crown-4 and derivatives thereof; wherein, the benzo 15-crown-5 derivative is obtained by replacing hydrogen on a benzo 15-crown-5 benzene ring by one of hydroxyl, amino, hydroxymethyl and amino-substituted methyl; the dibenzo 14-crown-4 derivative is obtained by substituting hydrogen on a benzene ring at one side of the dibenzo 14-crown-4 by one of hydroxyl, amino, hydroxymethyl and amino-substituted methyl.
2. The method for selectively separating lithium from the leachate of the positive electrode material of the waste lithium ion battery as claimed in claim 1, wherein: the organic solvent in the step (1) is one of sulfonated kerosene, dichloromethane, n-heptane, cyclohexane and nitrobenzene.
3. The method for selectively separating lithium from the leachate of the positive electrode material of the waste lithium ion battery as claimed in claim 2, wherein: the mass percentage of the crown ether compound in the organic solvent is 10-30%.
4. The method for selectively separating lithium from the leachate of the positive electrode material of the waste lithium ion battery as claimed in claim 1, wherein: the positive electrode material in the step (2) is one or a combination of two or more of lithium cobaltate, lithium manganate, lithium nickelate, a ternary positive electrode material and a lithium iron phosphate positive electrode material.
5. The method for selectively separating lithium from the leachate of the positive electrode material of the waste lithium ion battery as claimed in claim 4, wherein: the leaching solution in the step (2) is a filtrate obtained by leaching the cathode material in hydrochloric acid, sulfuric acid or nitric acid.
6. The method for selectively separating lithium from the leachate of the positive electrode material of the waste lithium ion battery as claimed in claim 5, wherein: the leachate in the step (2) contains 0.5-10g/L of Li, 0-80 g/L of Co, 0-80 g/L of Ni, 0-80 g/L of Mn 0-80 g/L and 0-80 g/L of Fe, and the concentration of hydrogen ions is 10-6～6mol/L。
7. The method for selectively separating lithium from the leachate of the positive electrode material of the waste lithium ion battery as claimed in claim 1, wherein: and (3) adopting single-stage extraction, 2-10-stage multi-stage cross-flow extraction or 2-10-stage multi-stage counter-current extraction in the step (2).
8. The method for selectively separating lithium from the leachate of the positive electrode material of the waste lithium ion battery as claimed in claim 1, wherein: in the step (2), the extraction temperature is 25-80 ℃, the extraction ratio is 1 (0.5-5), and the extraction time is 10-60 min.
9. The method for selectively separating lithium from the leachate of the positive electrode material of the waste lithium ion battery as claimed in claim 1, wherein: the temperature of back extraction-precipitation in the step (3) is 25-95 ℃, the volume ratio of the saturated sodium carbonate solution to the lithium-rich organic phase is 1 (0.5-2), and the time is 10-60 min.
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| US9147918B2 (en) * | 2011-05-27 | 2015-09-29 | Empire Technology Development Llc | Effective recovery of lithium from lithium ion battery waste |
| CN103785358A (en) * | 2012-11-02 | 2014-05-14 | 华东理工大学 | Materials used for extracting lithium from brine, and method |
| CN104241724B (en) * | 2014-09-02 | 2017-04-05 | 湖南邦普循环科技有限公司 | A kind of method for preparing battery-level lithium carbonate from lithium ion battery regenerant |
| CN107058742B (en) * | 2017-04-01 | 2019-02-22 | 司马忠志 | A method of lithium is recycled from waste and old lithium ion battery |
| CN107686892A (en) * | 2017-08-26 | 2018-02-13 | 冯小龙 | A kind of method for extracting lithium from waste water using extraction |
| CN108018436A (en) * | 2017-12-04 | 2018-05-11 | 青海柴达木兴华锂盐有限公司 | Extract lithium without saponification process |
| CN108486378A (en) * | 2018-03-14 | 2018-09-04 | 中国科学院过程工程研究所 | A kind of processing method of the leachate of waste material containing lithium electrode |
| CN108384955A (en) * | 2018-03-20 | 2018-08-10 | 中国科学院过程工程研究所 | A method of from selectively carrying lithium in waste material containing lithium battery |
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